An Energy Investigation into 1D/2D Oriented‐Attachment Assemblies of 1D Ag Nanocrystals

In the field of oriented‐attachment crystal growth, one‐dimensional nanocrystals are frequently employed as building blocks to synthesize two‐dimensional or large‐aspect‐ratio one‐dimensional nanocrystals. Despite recent extensive experimental advances, the underlying inter‐particle interaction in the synthesis still remains elusive. In this report, using Ag as a platform, we investigate the van der Waals interactions associated with the side‐by‐side and end‐to‐end assemblies of one‐dimensional nanorods. The size, aspect ratio, and inter‐particle separation of the Ag precursor nanorods are found to have dramatically different impacts on the van der Waals interactions in the two types of assemblies. Our work facilitates the fundamental understanding of the oriented‐attachment assembling mechanism based on one‐dimensional nanocrystals.     

Characterization of chitosan microparticles reinforced cellulose biocomposite sponges regenerated from ionic liquid

The chitosan-microparticles reinforced cellulose biocomposite sponges regenerated from ionic liquid were prepared and characterized. Fourier transform infrared (FTIR) spectroscopy confirmed that the cellulose dissolved in 1-allyl-3-methylimidazolium chloride without derivatization. Chitosan particles as reinforcement were incorporated into the cellulose matrix. FTIR spectra indicated hydrogen bonding between hydroxyl groups of cellulose and chitosan. The biocomposite sponges showed uniform three-dimensional interconnected porous structures. The breaking strength of the sponges increased significantly, from 0.09 to 0.32 MPa with the addition of 1.0 wt% chitosan. The sponges also demonstrated excellent antibacterial activity against S. aureus and E. coli with the average inhibition zone diameters >2 mm and the inhibition rate higher than 80 %. Furthermore, the biocomposite sponges exhibited good moisture penetrability and high porosity. The water uptake ability of the sponge was >25 times of its weight in water with a fast swelling. The chitosan/cellulose composite sponge is expected to be a promising material for potential applications as wound dressing.     

紫外分光光度法同时测定喹啉、吲哚、联苯的含量

采用了紫外分光光度法同时对喹啉、吲哚、联苯3组分的含量进行测定。根据喹啉、吲哚、联苯的紫外吸收光谱特征,确定266,290和313nm 3个波长作为测定波长。研究表明,在0~12 mg/L范围内,浓度和吸光度呈良好线性关系;266,290和313nm波长处喹啉、吲哚、联苯的吸光度具有较好的加和性,适用于多组分的同时测定;喹啉、吲哚、联苯的相对标准偏差分别为1.6%,1.0%,0.76%,采用标准加入法对3种物质进行了回收实验,回收率分别为98.5%~100.6%,97.5%~101.8%,98.8%~102.0%。     

Determination of bisphenol A, 4‐octylphenol,and 4‐nonylphenol in soft drinks and dairy products by ultrasound‐assisted dispersive liquid–liquid microextraction combined with derivatization and high‐performance liquid chromatography with fluorescence detection

A novel hyphenated method based on ultrasound‐assisted dispersive liquid–liquid microextraction coupled to precolumn derivatization has been established for the simultaneous determination of bisphenol A, 4‐octylphenol, and 4‐nonylphenol by high‐performance liquid chromatography with fluorescence detection. Different parameters that influence microextraction and derivatization have been optimized. The quantitative linear range of analytes is 5.0–400.0 ng/L, and the correlation coefficients are more than 0.9998. Limits of detection for soft drinks and dairy products have been obtained in the range of 0.5–1.2 ng/kg and 0.01–0.04 μg/kg, respectively. Relative standard deviations of intra‐ and inter‐day precision for retention time and peak area are in the range of 0.47–2.31 and 2.76–8.79%, respectively. Accuracy is satisfactory in the range of 81.5–118.7%. Relative standard deviations of repeatability are in the range of 0.35–1.43 and 2.36–4.75% for retention time and peak area, respectively. Enrichment factors for bisphenol A, 4‐octylphenol, and 4‐nonylphenol are 170.5, 240.3, and 283.2, respectively. The results of recovery and matrix effect are in the range of 82.7–114.9 and 92.0–109.0%, respectively. The proposed method has been applied to the determination of bisphenol A, 4‐octylphenol, and 4‐nonylphenol in soft drinks and dairy products with much higher sensitivity than many other methods.     

Recyclable polymer-based nano-hydrous manganese dioxide for highly efficient Tl(I) removal from water

Tl(I)in water even at a trace level is fatal to human beings and the ecosystem.Here we fabricated a new polymer-supported nanocomposite(HMO-001)for efficient Tl(I)removal by encapsulating nanosized hydrous manganese dioxide(HMO)within a polystyrene cation exchanger(D-001).The resultant HMO-001 exhibited more preferable removal of Tl(I)than D-001 and IRC-748,an iminodiacetic chelating polymer,particularly in the presence of competing Ca(II)ions at greater levels in solution.Such preference was ascribed to the Donnan membrane effect caused by D-001 as well as the specific interaction between Tl(I)and HMO.The adsorbed Tl(I)was partially oxidized into insoluble Tl(III)by HMO at acidic pH,while negligible oxidation was observed at circumneutral pH.The exhausted HMO-001 was amenable to efficient regeneration by binary NaOH-NaClO solution for at least 10-cycle batch runs without any significant capacity loss.Fixed-bed column test of Tl(I)-contained industrial effluent and natural water further validated that Tl(I)retention on HMO-001 resulted in a conspicuous concentration drop from 1.3 mg/L to a value lower than 0.14 mg/L(maximum concentration level for industrial effluent regulated by US EPA)and from 1–4?g/L to a value lower than 0.1?g/L(drinking water standard regulated by China Health Ministry),respectively.     

Gas Sorption Studies on a Microporous Coordination Polymer Assembled from 2D Grid Layers by Strong π–π Interactions

The microporous coordination polymer [Co(H₂L)(bipy)_0.5] ? 2 H₂O ( 1 , bipy=4,4′‐bipyridine) was synthesized on the basis of the V‐shaped flexible diphosphonate ligand (2,4,6‐trimethyl‐1,3‐phenylene)bis(methylene)diphosphonic acid (H₄L) and the auxiliary bipy ligand under hydrothermal conditions. The structure of this compound was characterized by single‐crystal X‐ray diffraction. By joining the diphosphonate ligands and bipy through tetrahedral [CoO₃N] clusters, a 2D square grid layered network was formed. Further stacking of these layers on the basis of π–π interactions resulted in a pseudo‐3D microporous network with 1D channels running through the a axis. Gas sorption studies for CO₂, H₂, CH₄, N₂, and O₂ on this coordination polymer were performed, and the results revealed interesting dynamic and hysteresis sorption behavior toward H₂ at low temperature.     

A Simple and Efficient Palladium Catalyst of Nitrogen-Based Ligand for Cu(I)- and Amine-Free Sonogashira Reaction

Glycine, as a kind of commercially available and inexpensive ligand, is used to prepare an air-stable and water-soluble catalyst used in Sonogashira reaction in our study. In the presence of 1% [PdCl₂(NH₂CH₂COOH)₂] as catalyst, excellent catalytic activity towards the Sonogashira coupling of aryl iodides with terminal alkynes without using any additive such as Cu(I)-cocatalyst is observed in a mixture of water and acetone (3/3 mL) under air at 60 °C with NaOH as a base, giving products in good to excellent yields.     

An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G(d,p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H₂O₂, is 1.17 × 10⁴⁸, which is consistent with the theoretical equilibrium constant is 2.18 × 10⁴⁸ at B3LYP/6-31++G(d,p)-IEFPCM level.     

Quantile estimations via modified Cholesky decomposition for longitudinal single-index models

Quantile regression is a powerful complement to the usual mean regression and becomes increasingly popular due to its desirable properties. In longitudinal studies, it is necessary to consider the intra-subject correlation among repeated measures over time to improve the estimation efficiency. In this paper, we focus on longitudinal single-index models. Firstly, we apply the modified Cholesky decomposition to parameterize the intra-subject covariance matrix and develop a regression approach to estimate the parameters of the covariance matrix. Secondly, we propose efficient quantile estimating equations for the index coefficients and the link function based on the estimated covariance matrix. Since the proposed estimating equations include a discrete indicator function, we propose smoothed estimating equations for fast and accurate computation of the index coefficients, as well as their asymptotic covariances. Thirdly, we establish the asymptotic properties of the proposed estimators. Finally, simulation studies and a real data analysis have illustrated the efficiency of the proposed approach.

     

甲基苯丙胺对微囊藻生长效应的动力学研究及机理初探

研究了不同浓度甲基苯丙胺在不同pH值条件下对铜绿微囊藻的生长效应及其动力学过程，并用色谱法对其作用机理进行了初步探讨．结果表明，在pH8．O，甲基苯丙胺浓度为0．2，2．0，20．0mg／L时，对微囊藻生长分别表现出促进、部分抑制和完全抑制效应；而在pH6．0时，3个浓度的甲基苯丙胺对微囊藻生长均表现出抑制效应，且随浓度的增大抑制效应增强．色谱分析结果表明，低浓度(0．2mg／L)的甲基苯丙胺促进了微囊藻的生长代谢，而高浓度(20．0mg／L)的甲基苯丙胺则损伤微囊藻细胞，抑制其生长代谢．